Up-grading hydrocarbons



United States Patent O 3,l2l,676 .UP-GRADHNG HYBRCARBNS Frank W. Slnaba, Sweeny, Tex., assigner to llsiilips Petroleum Company, a corporation of Delaware Filed Aug. l?, 1961, Ser. No. l32,lt94 3 Claims. (Cl. 20S- 62) This invention relates to a process and apparatus for up-grading hydrocarbon mixtures. In one of its aspects, it relates to a novel combination of steps comprising reforming, fractionation, solvent extraction, hydrogenation, and isomerization. In another aspect, the invention relates to a process and apparatus for 11p-grading hydrocarbons which comprises reforming a rst feed stream in a first low end-point reforming zone to produce a rst reformate stream, solvent extracting said ii-rst reformate stream to produce an extract stream comprising benzene and toluene and a raliinate stream comprising paratiins and naphthenes, separating said extract stream into a high-purity benzene product stream and a highpurity toluene product stream, separating said raiiinate stream into a parain-containing product stream and a first napthene-containing stream, hydrogenating and isomerizing said iirst naphthene-containing stream, separating from the thus hydrogenated and isomerized strea-m a high-purity cyclohexane product, reforming a second feed stream in a high end-point reforming zone to produce a second reformate stream, and admixing said second reformate stream with said first reformate stream. yIn still another aspect, the invention relates to process and apparatus for producing benzene, toluene, and cyclohexane from commonly available refinery streams.

Because of the rapid and relatively recent of the pertrochemical industry, demand for certain bulk chemicals of relatively high-purity has increased to the point Where it is more economically attractive to produce these chemicals than others which were in former demand. Among these chemicals of present demand are benzene, toluene, and cyclohexane. As known to the art, these chemicals are valuable for example as solvents, reaction media, and polymer starting materials. There is a substantial need in the art for processes and apparatus suitable for producing increasing quantities of these named chemicals from commonly available refinery streams.

Accordingly, it is an object of this invention to provide process and apparatus for producing quantities of 'benzene, toluene, and cyclohexane. It is another object of this invention t-o provide a novel combination of steps whereby commonly available refinery streams can be processed to produce increased quantities of relatively high-purity benzene, toluene, and cyclohexane.

Other aspects, obiects, and the several advantages of the invention will become apparent to one skilled in the art upon study of lthis disclosure, drawing, and appended claims.

According to my invention there is provided a process and apparatus for upgrading hydrocarbons which cornprises reforming a first feed stream in a iirst low endpoint reforming zone to produce a iirst reformate stream, solvent extracting said iirst reformate stream to produce an extract stream comprising benzene and toluene and a rathnate stream comprising paraflins and naphthenes, separating said extract stream into a high-purity benzene product stream and a high-purity toluene product stream, separating said raffinate stream into a paraffincontaining product stream and a first naphthene-contain ing stream, hydrogenating and isomerizing said tirs-t naphthene-containing stream, separating from the thus hydrogenated and isomerized stream a high-purity cyclohexane product, reforming a second feed stream in a high ice end-point reforming zone to produce a second reformate stream, and admixing said second reformate stream with said first reformate stream.

For a more complete understanding of my invention, reference is now made to the accompanying drawing Iwhich represents in schematic detail a presently-preferred form of my invention.

Referring to the drawing, a feed l which can be a high end-point naphtha is passed by Way of conduit l to a high endpoint reforming zone 3. Zone 3 is operated, as known in the art, to convert paratlins and napthenes present in the feed to aromatics, and can comprise Platforming, Ult-raforming, Houdriforming, or other known reforming operations. The reformate is passed by Way of conduit il, wherein it is mixed with a second reformate as will be discussed later, to a separation zone 5. ln this zone 5, excess hydrogen resulting from the reforming is removed by Way of conduit 6 and the lighter' fractions of the reformate, for example C5 and lighter hydrocarbons, are removed by way of conduit 7'. The resulting stream, comprising a mixture of C6 and heavier paraflins, naphthenes, and aromatics with small amounts of olefin, is passed by way of conduit S to a deheptanizing fractionator 9, wherein a stream comprising the C8 and heavier hydrocarbons is removed by way of conduit lil, and can be utilized as a gasoline prod uct or, for example, as a blending stock. The remaniing ream comprises `C., and C7 parafiins, naphthenes, and aromatics and is passed by Way of conduit lll to a solvent extraction zone l2. This zone can comprise one f the many processes for selective separation of hydrocarbon types, such as extraction with liquid SO2, The aromatic extract stream thus produced is passed by way of conduit lf3 to a fractionator 14, and is there separated into a high-purity benzene product stream. removed by way of conduit `l5 and a high-purity toluene product stream removed by Way of conduit i6. The ratiinate stream from zone l2 is passed by way of conduit i7 to a fractionator l5. This stream comprises C6 and C7 paraf- -tius and naphthenes, and is separated in fractionator 18 to produce a methylcyclopentane-and-lighter stream removed by way of conduit Ztl and a residual product suitable, `for example, as a gasoline blending stock, removed by way of conduit i9. The overhead in conduit 2l? is mixed with other later-described streams from conduits 2l and Si), and then passed to a fractionator 22. Here a relatively pure insohexane product is removed overhead by way of conduit 23, and the residue of this stream is passed by Way of conduit 24 to a hydrogenation zone 25. Excess hydrogen, for example from conduit d, is utilized here to effect saturation of any residual unsaturation in the stream, and results primarily in formation of cyclohexane from benzene. rifhe resulting stream is passed by Way of conduit 26 to isomerization zone Z7, wherein generally normal paraiiins are isomerized to isoparafns, and alkyl napthenes are isomerized to unsubstituted naphthenes. The isomerized stream is passed by Way of conduit 23 to a fractionator 29, wherein methylcyclopentane and lighter lis passed by way of conduit :itl to conduit 2l, previously described. The bottoms from this fractionation is passed. by Way of conduit 3l to a fractionator 32, wherein a high-purity cyclohexane product is separated and passed to further utility by Way of conduit 33. A gasoline blending stock is recovered by way of conduit 3d.

A second feed material, which `can comprise for example a 300 F. end point straight run gasoline' and/or an impure (eig, cyclohexane stream is introduced to the process by way of conduit 2, and is admixed with a stream from conduit 44. rThis latter stream is obtained from anatural gas liquid stream which comprises a third feed stream passed to the process by way of conduit 39.

This third feed stream is separated in fractionator 40 into an isohexane and lighter stream removed by way of conduit 45 and a lresidual stream removed by way of conduit 41. Stream 45 can be lfurther separated, if desired, in fractionator 46 into a stream comprising isopentane removed by way of `conduit 47 and a gasoline blending stock removed by lway of conduit d8. Residual stream 41 is deoilefd in fractionator 4.2, with the heavy ends being removed by way of conduit 43` and the center cut of the feed being passed by way of conduit 44 to conduit 2, wherein it is admixed, as previously stated, with the -second feed. The admixed stream is passed to a fractionator 35, wherein methylcyclopentane and lighter are removed overhead and passed by way of conduit 21 to fractionator 22 as previously described. The bottoms from fractionator 3S are passed by way of conduit 36 to a low end-point reforming Zone 37, which can be a reforming process similar to that described in conjunction with high end-point reforming zone 3. The reformate from zone 37 is passed by way of conduit 38 to conduit 4 wherein it is admixed with reformate from Zone 3 and further processed as previously described.

Thus, it can be seen that the plural reforming operations processing, as it were, special cuts of common refinery feeds combine to produce a stream rich in parafiins, aromatics, and naphthenes which in turn is separated by solvent extraction to yield an extract of the desired highpurity aromatics and a rafnate which is hydrogenated and isomerized to yield, after separation, a desired highpurity naphthene.

Example The ylow end point reforming (Platforming) operation is operated in the temperature range of 700 to 1000c F., preferably at about 800 to 950 F., and in a pressurerange of to 1000 psig., preferably 200 to 600 p.s.i.g. The hydrogen used is usually 0.5 to 20 mols per mol of feed, preferably l to 6. The catalyst is preferably a platinumtype reforming catalyst, that is, allumina impregnated with between 0.1 and weight percent platinum, preferably 0.1 to 1 weight percent, and containing iiuorine.

.T he high end point reforming (P'latforming) operation is operated in the temperature range of 700 to 1000 F., preferably at about 800 to 950 F., and in a pressure range of 0 to 1000 p.s.i.g., preferably 300 to 700 p.s.i.g. The hydrogen used is usually l to mols per mol of feed, preferably 2 to 10. The catalyst is the same as described with respect to the low end point reforming operation.

Benzene hydrogenation is effected at temperatures ranging from 370 to 500 F., and at pressures ranging from 400 to 500 p.s.i.g., and hydrogen to aromatics mol ratios in the range of 5 :1 to 12:1. The catalyst used is a nickel hydrogenation catalyst, e.g., nickel on kieselguhn the nickel content ranging from 20 to 55 Weight percent nickel.

The isomerization process is effected in a temperature range of 80 to 170 F., and preferably 100 to 150 F.

The pressures -used are 160 to 200 p.s.i.g., preferably 170 to 190 p.s.i.g. The catalyst used is aluminum chloride complex promoted by hydrochloric acid.

.The solvent extraction and fractionation steps are operated as known in the art to make the disclosed separations.

Conduit 1 (to high end point reformer):

Barrels per day 11,000

API at 60 F./60 F 54.6

Composition, vol. percent- Paraf'dncs 58.0 Naphthenics 40.0 Aromatics 12.0

Conduit 36 (to low end point reformer):

Barrels per day 13,000

API at 60 F./60 F 59.0

Composition, vol. percent- Parafnics 43.0 Naphthenics 50.0 Aromatics 7.0

Reasonable variation and modification are possible within the scope of this disclosure, the appended claims, and the drawing of the invention, the essence of which is that there is provided process and apparatus for up-grad ing mixed hydrocarbons comprising a plurality of reform ing steps, .solvent extraction of the mixed reformate, sep, aration of the resulting extract phase to produce hi-ghpurity aromatics, and hydrogenation, isomerization, and fractionation of the raffinate phase to produce high-purity naphthenes, along with advantageous recycles of various streams.

I claim:

l. A process for up-grading a plurality of hydrocarbon mixtures into a high purity cyclohexane, valuable aromatics and gasoline components which comprises the steps of:

(a) in a first reforming zone (3), reforming a feed (1) comprising a high end point naphtha reforming feed containing parains, naphthenes and aromatics;

(b) separating (35) another feed (2) comprising at least one of an impure cyclohexane containing stream and a low end boiling point straight-run gasoline, having an approximate end boiling point of about 300 F., into a methylcyclopentane-and-lighter stream (21) and a residue stream containing parans, naphthenes and aromatics (36);

(c) reforming (37) the residue stream obtained in step b;

(d) admixing the reformates of steps a and c (4);

(e) separating 5, 9) the admixed reformates of step d into a hydrogen containing product stream (6), a C5-and-lighter product stream (7), a Grand-heavier gasoline product (10) and a C-containing stream (11);

(f) separating by solvent extraction (12) the CG-containing stream of step e into a benzene and toluene containing extract product stream (13) and a parainand naphthene-containing rainate stream (17);

(g) separating (18) the rainate stream of step f into a methylcyclopentane-and-lighter containing stream (20) and a gasoline product stream (19);

(h) admixing the methylcyclopentane-and-lighter containing streams (21 and 20) obtained in steps b and g and with a further stream obtained as described later herein;

() separating (22) the admixed streams of step lz into an iso-hexane containing product stream (23) and a napththenes and parains containing stream also containing benzene (24);

(j) hydrogenating (25) the benzene contained in the last-mentioned stream of step i and isomerizing methylcyclopentane in said naphthenes contained in the last-mentioned stream of step i (27);

3,121,676 s 6 l (k) separating (29) the efuent (28) of step j into 3. A process according to claim 1 wherein a feed corna methylcyclopentane-and-lighter containing stream prising a de-isohexanized, de-oiled natural gas liquids (30) and a cyclohexane containing stream (31), the stream is admixed with the feed to step b. said methylcyclopentane-and-lighter stream (30) being the stream admixed with other streams in step 5 References Cited ill the 51e 0f this Patent 11, and recovering said cyclohexane. 2. The process according to claim 1 wherein a high UNITED STATES PATENTS purity cyclohexane is recovered from the cyclohexane con- 2,913,393 Sarno Nov. 17, 1959 taining stream (31) of step k by separating (32) the 3,009,002 Krom Nov. 14, 1961 same into a high purity cyclohexane (33) and a gasoline 10 3,013,088 Merryeld Dec. 12, 1961 fraction (34). 

1. A PROCESS FOR UP-GRADING A PLURALITY OF HYDROCARBON MIXTURES INTO A HIGH PURITY CYCLOHEXANE, VALUABLE AROMATICS AND GASOLINE COMPONENTS WHICH COMPRISES THE STEPS OF: (A) IN A FIRST REFORMING ZONE (3), REFORMING A FEED (1) COMPRISING A HIGH END POINT NAPHTHA REFORMING FEED CONTAINING PARAFFINS, NAPHTHENES AND AROMATICS; (B) SEPARATING (35) ANOTHER (2) COMPRISING AT LEAST ONE OF AN IMPURE CYCLOHEXANE CONTAINING STREAM AND A LOW END BOILING POINT STRAIGHT-RUN GASOLINE, HAVING AN APPROXIMATE END BOILING POINT OF ABOUT 300*F., INTO A METHYLCYCLOPENTANCE-AND-HIGHER STREAM (21) AND A RESIDUE STREAM CONTAINING PARAFFINS, NAPHTHENES AND AROMATICS (36); (C) REFORMING (37) THE RESIDUE STREAM OBTAINED IN STEP "B"; (D) ADMIXING THE REFORMATES OF STEPS "A" AND "C" (4) (E) SEPARATING 5,9) THE ADMIXED REFORMATES OF STEP "D" INTO A HYDROGEN CONTAINING PRODUCT STREAM (L), A C5-AND-LIGHTER PRODUCT STREAM (7), A C7-AND HEAVIER GASOLINE PRODUCT (10) AND A C6-CONTAINING STREAM (11); (F) SEPARATING BY SOLVENT EXTRACTION (12) THE C6-CONTAINING STREAM OF STEP "E" INTO A BENZENE AND TOLUENE CONTAINING EXTRACT PRODUCT STREAM (13) AND A PARAFFIN-AND NAPHTHENE-CONTAINING RAFFINATE STREAM (17); (G) SEPARATING (18) THE RAFFINATE STREAM OF STEP "F" INTO A METHYLCYCLOPENTANE-AND-LIGHTER CONTAINING STREAM (20) AND A GASOLINE PRODUCT STREAM (19); 